Acrylonitriles diketone reaction

SMP is a useful chiral auxiliary in various cycloaddition reactions. Chiral 2-amino-1,3-dienes have been used in the Diels-Alder reaction with 2-aryl-1 -nitroethylenes, and 5-ary 1-2-methyl-substituted 4-nitrocyclohexanones were obtained in excellent enantiomeric purities (ee=95-99%) and diastereoselectiv-ities (ds = 75-95% eq 6). The photo-Diels-Alder reaction of SMP acrylonitrile with 1-acetylnaphthalene has been carried out. After hydrolysis of the adduct, the 1,4-diketone was obtained in excellent enantiomeric purity (ee > 97% eq 7). 

Addition of a-aminonitriles to an a,p-unsaturated ketone affords 1,4-diketones. High yields are also observed in 1,4-additions to ethyl acrylate or acrylonitrile. o-Phenyl-a-(A -morpholino)acetonitrile gives good yields of 1,4-adducts with methyl crotonate, methyl methacrylate, diethyl maleate and ethyl propiolate under catalysis of sodium methoxide in THF. Reaction of the lithium salt of (41) with methyl acrylate is reported to give pyrrole derivatives (Scheme 18). 

The reaction did not require dry solvents or inert atmosphere and afforded the desired adducts in 42-98% yield. As expected, the more reactive acrolein and methyl vinyl ketone gave very good results with both acyclic and cyclic p-ketoesters and p-diketones and, surprisingly, acrylonitrile and methyl acrylate, reported to be totally inactive under Lewis acid catalysis, " afforded the corresponding adducts with a-acetylbutyrolactone in high yield (77 and 98% respectively). In the reaction with crotonaldehyde, a 1 1 mixture of... 

A metalloid template has been used in the synthesis of some triazepinones and triazepinethiones thus, for example, the reaction of acyclic diamines with dimethylsilicon isocyanate gave (212) after its reaction with thiocarbonyl diimidazole and subsequent hydrolytic removal of the silicon template, (212) gave (213)/ Aminohydroxy-l,2,4-triazepines (214 R = H or Me) have been prepared in high yield by the addition of aminoguanidine to acrylonitrile and related unsaturated esters.Condensation of )8-keto-esters with 1,2-diamino-imidazoles gave mainly imidazotriazepinones, e.g. (215), but with jS-diketones O... 

Although ketones are not generally considered to be reactive carbonyl partners in MBH reactions (except under high pressure), the enhanced reactivity of certain a-diketones towards aldol-type reactions make them suitable partners for reaction with MBH-type vinyl carbanion equivalents. Indeed, a-keto esters have been found to possess the requisite reactivity and are very reactive electrophiles for the MBH reaction of acrylate, methyl vinyl ketone, acrylonitrile and acrolein in the presence of a tertiary amine, such as DABCO (Scheme 1.66). " ... 

The MBH reactions of non-enolizable a-diketones precursors (Figure 1.4) with the activated olefins, e.g. acrolein, methyl acrylate and acrylonitrile, have been investigated systematically. The reaction of 3,3,5,5-tetramethyl-cyclopentane-l,2-dione (162) with acrolein and acrylonitrile, but not methyl acrylate, afforded the mono-a-hydroxyalkylation products in high yields. Other nonenolizable a-diketones, such as camphorquinone (159), homo-adamantane-2,3-dione (160) and bicyclo[ 3.3.2]decane-9,10-dione (161) reacted only with acrylonitrile, probably due to the hindered nature of the a-dicarbonyl compounds and the difference in steric demand between nitrile and ester. 

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